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Dimethyl (3,4-dichlorobenzoyl)carbonohydrazonodithioate, C10H10Cl2N2OS2, (D1), dibenzyl (3,4-dichlorobenzoyl)carbonohydrazonodithioate, C22H18Cl2N2OS2, (D2), dimethyl (3,4-dichlorobenzoyl)-1-methylcarbonohydrazonodithioate, C11H12Cl2N2OS2, (D3), 3,4-dichloro-N'-(1,3-dithiolan-2-ylidene)-N-methylbenzohydrazide, C11H10Cl2N2OS2, (D4), were synthesized as potential tuberculostatics. Compound (D1) (with two molecules in the asymmetric unit) was the only one showing tuberculostatic activity of the same range as the common drugs isoniazid and pyrazinamide. The molecular structures of the studied compounds depend on the substitution at the N atom adjacent to the carbonyl group. In the case of the unsubstituted derivatives (D1) and (D2), their central frames are generally planar with a twist of the 3,4-dichlorophenyl ring by 30-40°. Until now, coplanarity of the aromatic ring with the (methylene)carbonohydrazone fragment has been considered a prerequisite for tuberculostatic activity. The N-methylated derivatives (D3) and (D4) show an additional twist along the N-C(=O) bond by 20-30° due to the spatial repulsion introduced by the methyl substituent.
Supporting information
CCDC references: 873884; 873885; 873886; 873887
The synthesis of (D1) was described previously by Gobis et al.
(2011). The other compounds were obtained from 3,4-dichlorobenzohydrazide [for
(D2)] or 3,4-dichloro-N-methylhydrazide [for (D3) and
(D4)] according to the same method. Benzohydrazides were dissolved in a
methanol solution of triethylamine and treated with carbon disulfide and the
respective halide, viz. methyl iodide for (D3), benzyl chloride
for (D2) or ethylene bromide for (D4). Single crystals of
(D1), (D2), (D3) and (D4) suitable for X-ray
diffraction were obtained from ethanol solutions by slow evaporation of the
solvents at room temperature.
H atoms were located in difference Fourier maps and subsequently geometrically
optimized and allowed for as riding atoms, with C—H = 0.93 Å for aromatic
CH groups, 0.97 Å for secondary CH2 groups and 0.96 Å for methyl groups,
N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C,N).
Data collection: APEX2 (Bruker, 2002) for D1, D4; CrysAlis CCD (Oxford Diffraction, 2008) for D2, D3. Cell refinement: SAINT-Plus (Bruker, 2003) for D1, D4; CrysAlis RED (Oxford Diffraction, 2008) for D2, D3. Data reduction: SAINT-Plus (Bruker, 2003) for D1, D4; CrysAlis RED (Oxford Diffraction, 2008) for D2, D3. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).
(D1) Dimethyl (3,4-dichlorobenzoyl)carbonohydrazonodithioate
top
Crystal data top
C10H10Cl2N2OS2 | F(000) = 632 |
Mr = 309.22 | Dx = 1.516 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 9897 reflections |
a = 9.2225 (4) Å | θ = 2.4–29.7° |
b = 11.2741 (5) Å | µ = 0.77 mm−1 |
c = 13.0892 (5) Å | T = 296 K |
β = 95.367 (1)° | Plate, colourless |
V = 1354.99 (10) Å3 | 0.3 × 0.3 × 0.1 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD diffractometer | 7766 independent reflections |
Radiation source: fine-focus sealed tube | 7138 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scan | θmax = 29.8°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −12→12 |
Tmin = 0.914, Tmax = 1.000 | k = −15→15 |
33334 measured reflections | l = −18→18 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0521P)2 + 0.1856P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
7766 reflections | Δρmax = 0.79 e Å−3 |
312 parameters | Δρmin = −0.31 e Å−3 |
3 restraints | Absolute structure: Flack (1983), ???? Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (4) |
Crystal data top
C10H10Cl2N2OS2 | V = 1354.99 (10) Å3 |
Mr = 309.22 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.2225 (4) Å | µ = 0.77 mm−1 |
b = 11.2741 (5) Å | T = 296 K |
c = 13.0892 (5) Å | 0.3 × 0.3 × 0.1 mm |
β = 95.367 (1)° | |
Data collection top
Bruker SMART APEX CCD diffractometer | 7766 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 7138 reflections with I > 2σ(I) |
Tmin = 0.914, Tmax = 1.000 | Rint = 0.021 |
33334 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.092 | Δρmax = 0.79 e Å−3 |
S = 1.08 | Δρmin = −0.31 e Å−3 |
7766 reflections | Absolute structure: Flack (1983), ???? Friedel pairs |
312 parameters | Absolute structure parameter: −0.02 (4) |
3 restraints | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.30896 (5) | 0.00002 (5) | 0.86012 (4) | 0.04235 (10) | |
S2 | 0.41312 (6) | 0.00171 (5) | 1.08359 (4) | 0.05065 (12) | |
O5 | 0.73268 (13) | 0.22218 (15) | 0.85354 (11) | 0.0459 (3) | |
N2 | 0.49881 (17) | 0.15555 (15) | 0.95100 (12) | 0.0394 (3) | |
N3 | 0.48906 (15) | 0.19643 (15) | 0.84831 (12) | 0.0386 (3) | |
H3 | 0.4061 | 0.1994 | 0.8124 | 0.046* | |
Cl3 | 0.78955 (8) | 0.50855 (7) | 0.53377 (6) | 0.07311 (19) | |
Cl4 | 0.55301 (10) | 0.39896 (8) | 0.37062 (5) | 0.0796 (2) | |
C1 | 0.41683 (18) | 0.06603 (16) | 0.96262 (13) | 0.0341 (3) | |
C4 | 0.61023 (17) | 0.23034 (15) | 0.80782 (13) | 0.0332 (3) | |
C11 | 0.2299 (3) | −0.1285 (2) | 0.9157 (2) | 0.0619 (6) | |
H11A | 0.3060 | −0.1777 | 0.9478 | 0.093* | |
H11B | 0.1746 | −0.1727 | 0.8628 | 0.093* | |
H11C | 0.1670 | −0.1035 | 0.9661 | 0.093* | |
C21 | 0.5515 (4) | 0.0845 (4) | 1.1567 (2) | 0.0948 (12) | |
H21D | 0.6402 | 0.0808 | 1.1238 | 0.142* | |
H21E | 0.5676 | 0.0515 | 1.2244 | 0.142* | |
H21F | 0.5212 | 0.1656 | 1.1611 | 0.142* | |
C41 | 0.58754 (17) | 0.27608 (16) | 0.70005 (13) | 0.0339 (3) | |
C42 | 0.6826 (2) | 0.36172 (17) | 0.66960 (16) | 0.0399 (4) | |
H42 | 0.7546 | 0.3927 | 0.7167 | 0.048* | |
C43 | 0.6702 (2) | 0.40106 (18) | 0.56866 (17) | 0.0448 (4) | |
C44 | 0.5652 (3) | 0.3551 (2) | 0.49789 (16) | 0.0485 (4) | |
C45 | 0.4692 (2) | 0.2700 (2) | 0.52749 (15) | 0.0504 (5) | |
H45 | 0.3979 | 0.2391 | 0.4799 | 0.060* | |
C46 | 0.4798 (2) | 0.23091 (19) | 0.62859 (14) | 0.0425 (4) | |
H46 | 0.4147 | 0.1744 | 0.6487 | 0.051* | |
S1A | −0.01588 (7) | 0.10404 (5) | 1.03930 (4) | 0.05128 (13) | |
S2A | 0.18313 (6) | 0.28235 (5) | 1.15163 (4) | 0.04864 (12) | |
O5A | 0.21946 (13) | 0.29299 (15) | 0.76583 (11) | 0.0453 (3) | |
N2A | 0.11746 (16) | 0.28335 (15) | 0.95205 (11) | 0.0394 (3) | |
N3A | 0.04162 (15) | 0.23506 (16) | 0.86391 (11) | 0.0369 (3) | |
H3A | −0.0400 | 0.1990 | 0.8671 | 0.044* | |
Cl3A | −0.03349 (12) | 0.27259 (8) | 0.38492 (5) | 0.0869 (3) | |
Cl4A | −0.24765 (11) | 0.05505 (9) | 0.40157 (6) | 0.0921 (3) | |
C1A | 0.09641 (18) | 0.22930 (17) | 1.03549 (13) | 0.0355 (3) | |
C4A | 0.10054 (17) | 0.24678 (16) | 0.77423 (13) | 0.0337 (3) | |
C11A | 0.0027 (4) | 0.0564 (3) | 1.1690 (2) | 0.0697 (7) | |
H11D | 0.1042 | 0.0529 | 1.1932 | 0.105* | |
H11E | −0.0399 | −0.0208 | 1.1737 | 0.105* | |
H11F | −0.0459 | 0.1114 | 1.2102 | 0.105* | |
C21A | 0.2975 (3) | 0.3960 (2) | 1.10652 (19) | 0.0584 (6) | |
H21A | 0.3550 | 0.3633 | 1.0559 | 0.088* | |
H21B | 0.3607 | 0.4262 | 1.1630 | 0.088* | |
H21C | 0.2381 | 0.4592 | 1.0766 | 0.088* | |
C41A | 0.01085 (18) | 0.19624 (16) | 0.68325 (13) | 0.0352 (3) | |
C42A | 0.0258 (2) | 0.24797 (18) | 0.58829 (14) | 0.0428 (4) | |
H42A | 0.0898 | 0.3110 | 0.5832 | 0.051* | |
C43A | −0.0547 (3) | 0.2054 (2) | 0.50155 (15) | 0.0496 (5) | |
C44A | −0.1473 (3) | 0.1120 (2) | 0.50884 (17) | 0.0553 (5) | |
C45A | −0.1615 (3) | 0.0585 (2) | 0.60314 (19) | 0.0544 (5) | |
H45A | −0.2248 | −0.0051 | 0.6074 | 0.065* | |
C46A | −0.0814 (2) | 0.0998 (2) | 0.69042 (16) | 0.0449 (4) | |
H46A | −0.0893 | 0.0634 | 0.7534 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0440 (2) | 0.0435 (2) | 0.0386 (2) | −0.00481 (19) | −0.00149 (17) | −0.00038 (19) |
S2 | 0.0576 (3) | 0.0578 (3) | 0.0363 (2) | −0.0071 (3) | 0.00302 (19) | 0.0130 (2) |
O5 | 0.0262 (5) | 0.0689 (9) | 0.0421 (7) | 0.0028 (6) | 0.0002 (5) | 0.0006 (6) |
N2 | 0.0338 (7) | 0.0495 (9) | 0.0341 (7) | −0.0043 (6) | −0.0014 (5) | 0.0083 (6) |
N3 | 0.0291 (6) | 0.0528 (9) | 0.0329 (7) | −0.0053 (6) | −0.0032 (5) | 0.0115 (6) |
Cl3 | 0.0707 (4) | 0.0616 (3) | 0.0894 (5) | −0.0168 (3) | 0.0206 (3) | 0.0247 (3) |
Cl4 | 0.0990 (5) | 0.0949 (5) | 0.0450 (3) | 0.0032 (4) | 0.0076 (3) | 0.0258 (3) |
C1 | 0.0318 (7) | 0.0403 (8) | 0.0301 (7) | 0.0025 (6) | 0.0031 (6) | 0.0037 (6) |
C4 | 0.0288 (7) | 0.0355 (8) | 0.0351 (8) | −0.0005 (6) | 0.0020 (6) | 0.0004 (6) |
C11 | 0.0653 (15) | 0.0477 (12) | 0.0713 (16) | −0.0152 (11) | −0.0015 (12) | 0.0041 (11) |
C21 | 0.098 (2) | 0.134 (3) | 0.0460 (13) | −0.042 (2) | −0.0290 (14) | 0.0191 (17) |
C41 | 0.0300 (7) | 0.0366 (8) | 0.0353 (7) | −0.0002 (6) | 0.0035 (6) | −0.0003 (6) |
C42 | 0.0349 (8) | 0.0378 (9) | 0.0475 (10) | −0.0022 (7) | 0.0068 (7) | −0.0001 (7) |
C43 | 0.0453 (10) | 0.0395 (9) | 0.0514 (11) | −0.0009 (7) | 0.0144 (8) | 0.0090 (8) |
C44 | 0.0570 (11) | 0.0522 (11) | 0.0372 (9) | 0.0066 (9) | 0.0095 (8) | 0.0082 (8) |
C45 | 0.0494 (10) | 0.0630 (13) | 0.0375 (9) | −0.0051 (9) | −0.0030 (8) | 0.0021 (9) |
C46 | 0.0387 (8) | 0.0504 (10) | 0.0383 (9) | −0.0086 (8) | 0.0029 (7) | 0.0003 (8) |
S1A | 0.0588 (3) | 0.0507 (3) | 0.0424 (2) | −0.0166 (2) | −0.0056 (2) | 0.0046 (2) |
S2A | 0.0509 (3) | 0.0600 (3) | 0.0334 (2) | −0.0092 (2) | −0.00478 (18) | −0.0033 (2) |
O5A | 0.0287 (5) | 0.0632 (9) | 0.0440 (7) | −0.0033 (6) | 0.0041 (5) | 0.0075 (6) |
N2A | 0.0341 (7) | 0.0504 (8) | 0.0329 (7) | −0.0065 (6) | −0.0012 (5) | −0.0031 (6) |
N3A | 0.0265 (6) | 0.0519 (8) | 0.0318 (7) | −0.0042 (6) | 0.0004 (5) | −0.0020 (6) |
Cl3A | 0.1448 (8) | 0.0808 (5) | 0.0338 (3) | 0.0009 (5) | 0.0016 (3) | 0.0053 (3) |
Cl4A | 0.1035 (6) | 0.1088 (6) | 0.0583 (4) | −0.0104 (5) | −0.0234 (4) | −0.0303 (4) |
C1A | 0.0300 (7) | 0.0425 (8) | 0.0331 (8) | −0.0004 (7) | −0.0012 (6) | −0.0028 (7) |
C4A | 0.0260 (7) | 0.0412 (8) | 0.0336 (8) | 0.0053 (6) | 0.0006 (6) | 0.0027 (6) |
C11A | 0.105 (2) | 0.0596 (14) | 0.0440 (12) | −0.0181 (14) | 0.0059 (13) | 0.0118 (10) |
C21A | 0.0540 (12) | 0.0643 (14) | 0.0542 (12) | −0.0193 (11) | −0.0083 (10) | −0.0029 (11) |
C41A | 0.0308 (7) | 0.0415 (9) | 0.0334 (8) | 0.0051 (6) | 0.0028 (6) | −0.0022 (7) |
C42A | 0.0480 (10) | 0.0460 (10) | 0.0349 (9) | 0.0040 (8) | 0.0068 (7) | −0.0020 (7) |
C43A | 0.0634 (12) | 0.0533 (11) | 0.0317 (9) | 0.0106 (10) | 0.0022 (8) | −0.0029 (8) |
C44A | 0.0546 (11) | 0.0659 (14) | 0.0435 (10) | 0.0098 (10) | −0.0057 (9) | −0.0209 (10) |
C45A | 0.0536 (12) | 0.0565 (12) | 0.0525 (12) | −0.0103 (10) | 0.0025 (9) | −0.0149 (10) |
C46A | 0.0450 (9) | 0.0510 (10) | 0.0393 (9) | −0.0027 (8) | 0.0067 (7) | −0.0034 (8) |
Geometric parameters (Å, º) top
S1—C1 | 1.7589 (18) | S1A—C1A | 1.7547 (19) |
S1—C11 | 1.806 (2) | S1A—C11A | 1.773 (2) |
S2—C1 | 1.7447 (17) | S2A—C1A | 1.7552 (18) |
S2—C21 | 1.785 (3) | S2A—C21A | 1.794 (3) |
O5—C4 | 1.231 (2) | O5A—C4A | 1.228 (2) |
N2—C1 | 1.279 (2) | N2A—C1A | 1.281 (2) |
N2—N3 | 1.416 (2) | N2A—N3A | 1.402 (2) |
N3—C4 | 1.337 (2) | N3A—C4A | 1.345 (2) |
N3—H3 | 0.8600 | N3A—H3A | 0.8600 |
Cl3—C43 | 1.727 (2) | Cl3A—C43A | 1.732 (2) |
Cl4—C44 | 1.731 (2) | Cl4A—C44A | 1.731 (2) |
C4—C41 | 1.498 (2) | C4A—C41A | 1.498 (2) |
C11—H11A | 0.9600 | C11A—H11D | 0.9600 |
C11—H11B | 0.9600 | C11A—H11E | 0.9600 |
C11—H11C | 0.9600 | C11A—H11F | 0.9600 |
C21—H21D | 0.9600 | C21A—H21A | 0.9600 |
C21—H21E | 0.9600 | C21A—H21B | 0.9600 |
C21—H21F | 0.9600 | C21A—H21C | 0.9600 |
C41—C42 | 1.388 (2) | C41A—C46A | 1.389 (3) |
C41—C46 | 1.396 (2) | C41A—C42A | 1.392 (3) |
C42—C43 | 1.388 (3) | C42A—C43A | 1.383 (3) |
C42—H42 | 0.9300 | C42A—H42A | 0.9300 |
C43—C44 | 1.377 (3) | C43A—C44A | 1.365 (4) |
C44—C45 | 1.386 (3) | C44A—C45A | 1.391 (4) |
C45—C46 | 1.389 (3) | C45A—C46A | 1.382 (3) |
C45—H45 | 0.9300 | C45A—H45A | 0.9300 |
C46—H46 | 0.9300 | C46A—H46A | 0.9300 |
| | | |
C1—S1—C11 | 104.65 (11) | C1A—S1A—C11A | 105.45 (11) |
C1—S2—C21 | 101.27 (12) | C1A—S2A—C21A | 101.11 (10) |
C1—N2—N3 | 112.59 (15) | C1A—N2A—N3A | 114.40 (15) |
C4—N3—N2 | 119.23 (14) | C4A—N3A—N2A | 117.95 (14) |
C4—N3—H3 | 120.4 | C4A—N3A—H3A | 121.0 |
N2—N3—H3 | 120.4 | N2A—N3A—H3A | 121.0 |
N2—C1—S2 | 119.87 (14) | N2A—C1A—S2A | 118.89 (14) |
N2—C1—S1 | 122.80 (13) | N2A—C1A—S1A | 122.95 (14) |
S2—C1—S1 | 117.30 (10) | S2A—C1A—S1A | 118.16 (10) |
O5—C4—N3 | 123.28 (16) | O5A—C4A—N3A | 123.83 (16) |
O5—C4—C41 | 121.63 (15) | O5A—C4A—C41A | 121.44 (15) |
N3—C4—C41 | 115.05 (14) | N3A—C4A—C41A | 114.73 (15) |
S1—C11—H11A | 109.5 | S1A—C11A—H11D | 109.5 |
S1—C11—H11B | 109.5 | S1A—C11A—H11E | 109.5 |
H11A—C11—H11B | 109.5 | H11D—C11A—H11E | 109.5 |
S1—C11—H11C | 109.5 | S1A—C11A—H11F | 109.5 |
H11A—C11—H11C | 109.5 | H11D—C11A—H11F | 109.5 |
H11B—C11—H11C | 109.5 | H11E—C11A—H11F | 109.5 |
S2—C21—H21D | 109.5 | S2A—C21A—H21A | 109.5 |
S2—C21—H21E | 109.5 | S2A—C21A—H21B | 109.5 |
H21D—C21—H21E | 109.5 | H21A—C21A—H21B | 109.5 |
S2—C21—H21F | 109.5 | S2A—C21A—H21C | 109.5 |
H21D—C21—H21F | 109.5 | H21A—C21A—H21C | 109.5 |
H21E—C21—H21F | 109.5 | H21B—C21A—H21C | 109.5 |
C42—C41—C46 | 119.40 (17) | C46A—C41A—C42A | 120.06 (17) |
C42—C41—C4 | 118.26 (16) | C46A—C41A—C4A | 122.71 (16) |
C46—C41—C4 | 122.24 (16) | C42A—C41A—C4A | 117.21 (17) |
C43—C42—C41 | 119.81 (18) | C43A—C42A—C41A | 119.8 (2) |
C43—C42—H42 | 120.1 | C43A—C42A—H42A | 120.1 |
C41—C42—H42 | 120.1 | C41A—C42A—H42A | 120.1 |
C44—C43—C42 | 120.71 (18) | C44A—C43A—C42A | 120.1 (2) |
C44—C43—Cl3 | 120.77 (16) | C44A—C43A—Cl3A | 121.48 (17) |
C42—C43—Cl3 | 118.52 (17) | C42A—C43A—Cl3A | 118.40 (19) |
C43—C44—C45 | 120.01 (19) | C43A—C44A—C45A | 120.5 (2) |
C43—C44—Cl4 | 121.22 (17) | C43A—C44A—Cl4A | 121.3 (2) |
C45—C44—Cl4 | 118.75 (18) | C45A—C44A—Cl4A | 118.1 (2) |
C46—C45—C44 | 119.72 (19) | C44A—C45A—C46A | 120.0 (2) |
C46—C45—H45 | 120.1 | C44A—C45A—H45A | 120.0 |
C44—C45—H45 | 120.1 | C46A—C45A—H45A | 120.0 |
C45—C46—C41 | 120.33 (18) | C45A—C46A—C41A | 119.4 (2) |
C45—C46—H46 | 119.8 | C45A—C46A—H46A | 120.3 |
C41—C46—H46 | 119.8 | C41A—C46A—H46A | 120.3 |
| | | |
C1—N2—N3—C4 | −139.31 (18) | C1A—N2A—N3A—C4A | −150.87 (17) |
N3—N2—C1—S2 | 179.83 (13) | N3A—N2A—C1A—S2A | −179.09 (12) |
N3—N2—C1—S1 | 1.8 (2) | N3A—N2A—C1A—S1A | 0.8 (2) |
C21—S2—C1—N2 | −5.0 (2) | C21A—S2A—C1A—N2A | −6.41 (19) |
C21—S2—C1—S1 | 173.20 (18) | C21A—S2A—C1A—S1A | 173.66 (13) |
C11—S1—C1—N2 | 174.84 (17) | C11A—S1A—C1A—N2A | 175.46 (19) |
C11—S1—C1—S2 | −3.28 (15) | C11A—S1A—C1A—S2A | −4.61 (17) |
N2—N3—C4—O5 | 4.0 (3) | N2A—N3A—C4A—O5A | 3.1 (3) |
N2—N3—C4—C41 | −177.95 (16) | N2A—N3A—C4A—C41A | −178.19 (15) |
O5—C4—C41—C42 | −32.5 (3) | O5A—C4A—C41A—C46A | 148.78 (19) |
N3—C4—C41—C42 | 149.38 (17) | N3A—C4A—C41A—C46A | −30.0 (2) |
O5—C4—C41—C46 | 143.93 (19) | O5A—C4A—C41A—C42A | −29.5 (3) |
N3—C4—C41—C46 | −34.2 (2) | N3A—C4A—C41A—C42A | 151.70 (17) |
C46—C41—C42—C43 | −0.3 (3) | C46A—C41A—C42A—C43A | 2.0 (3) |
C4—C41—C42—C43 | 176.23 (17) | C4A—C41A—C42A—C43A | −179.69 (17) |
C41—C42—C43—C44 | −0.7 (3) | C41A—C42A—C43A—C44A | −0.8 (3) |
C41—C42—C43—Cl3 | 179.51 (15) | C41A—C42A—C43A—Cl3A | 179.76 (15) |
C42—C43—C44—C45 | 1.0 (3) | C42A—C43A—C44A—C45A | −0.2 (3) |
Cl3—C43—C44—C45 | −179.19 (17) | Cl3A—C43A—C44A—C45A | 179.23 (19) |
C42—C43—C44—Cl4 | −177.39 (16) | C42A—C43A—C44A—Cl4A | −178.97 (17) |
Cl3—C43—C44—Cl4 | 2.4 (3) | Cl3A—C43A—C44A—Cl4A | 0.4 (3) |
C43—C44—C45—C46 | −0.3 (3) | C43A—C44A—C45A—C46A | 0.0 (4) |
Cl4—C44—C45—C46 | 178.13 (18) | Cl4A—C44A—C45A—C46A | 178.86 (18) |
C44—C45—C46—C41 | −0.7 (3) | C44A—C45A—C46A—C41A | 1.1 (3) |
C42—C41—C46—C45 | 1.0 (3) | C42A—C41A—C46A—C45A | −2.1 (3) |
C4—C41—C46—C45 | −175.40 (18) | C4A—C41A—C46A—C45A | 179.65 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21E···Cl4Ai | 0.96 | 2.75 | 3.565 (3) | 144 |
N3A—H3A···O5ii | 0.86 | 2.10 | 2.8434 (18) | 144 |
N3—H3···O5A | 0.86 | 2.06 | 2.834 (2) | 149 |
N3—H3···S1 | 0.86 | 2.52 | 2.7810 (17) | 99 |
N3A—H3A···S1A | 0.86 | 2.49 | 2.8216 (16) | 104 |
Symmetry codes: (i) x+1, y, z+1; (ii) x−1, y, z. |
(D2) dibenzyl (3,4-dichlorobenzoyl)carbonohydrazonodithioate
top
Crystal data top
C22H18Cl2N2OS2 | F(000) = 1904 |
Mr = 461.40 | Dx = 1.401 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 21835 reflections |
a = 28.6760 (11) Å | θ = 2.0–36.3° |
b = 10.3705 (3) Å | µ = 0.50 mm−1 |
c = 14.7176 (6) Å | T = 292 K |
β = 90.900 (4)° | Prism, colourless |
V = 4376.2 (3) Å3 | 0.55 × 0.4 × 0.3 mm |
Z = 8 | |
Data collection top
Kuma KM-4 CCD diffractometer | 3868 independent reflections |
Radiation source: fine-focus sealed tube | 3021 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω and π scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | h = −34→31 |
Tmin = 0.942, Tmax = 1.000 | k = −12→12 |
17461 measured reflections | l = −17→17 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.061P)2] where P = (Fo2 + 2Fc2)/3 |
3868 reflections | (Δ/σ)max = 0.002 |
262 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Crystal data top
C22H18Cl2N2OS2 | V = 4376.2 (3) Å3 |
Mr = 461.40 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 28.6760 (11) Å | µ = 0.50 mm−1 |
b = 10.3705 (3) Å | T = 292 K |
c = 14.7176 (6) Å | 0.55 × 0.4 × 0.3 mm |
β = 90.900 (4)° | |
Data collection top
Kuma KM-4 CCD diffractometer | 3868 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 3021 reflections with I > 2σ(I) |
Tmin = 0.942, Tmax = 1.000 | Rint = 0.022 |
17461 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.22 e Å−3 |
3868 reflections | Δρmin = −0.29 e Å−3 |
262 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.89267 (5) | 0.29944 (17) | 0.81737 (11) | 0.0432 (4) | |
C4 | 0.90756 (6) | −0.01453 (16) | 0.73969 (11) | 0.0414 (4) | |
C11 | 0.88299 (7) | 0.47072 (18) | 0.67553 (14) | 0.0614 (5) | |
H11A | 0.8597 | 0.5087 | 0.7145 | 0.074* | |
H11B | 0.8967 | 0.5395 | 0.6401 | 0.074* | |
C12 | 0.85989 (6) | 0.37698 (16) | 0.61288 (12) | 0.0487 (4) | |
C13 | 0.81801 (7) | 0.3195 (2) | 0.63567 (14) | 0.0587 (5) | |
H13 | 0.8038 | 0.3417 | 0.6898 | 0.070* | |
C14 | 0.79741 (9) | 0.2307 (2) | 0.57976 (19) | 0.0800 (7) | |
H14 | 0.7695 | 0.1921 | 0.5959 | 0.096* | |
C15 | 0.81815 (12) | 0.1989 (3) | 0.4998 (2) | 0.0923 (9) | |
H15 | 0.8041 | 0.1387 | 0.4615 | 0.111* | |
C16 | 0.85962 (12) | 0.2548 (3) | 0.47545 (16) | 0.0873 (9) | |
H16 | 0.8735 | 0.2327 | 0.4209 | 0.105* | |
C17 | 0.88032 (8) | 0.3436 (2) | 0.53221 (14) | 0.0631 (6) | |
H17 | 0.9084 | 0.3815 | 0.5161 | 0.076* | |
C21 | 0.82591 (7) | 0.2802 (2) | 0.95176 (13) | 0.0656 (5) | |
H21A | 0.8395 | 0.1949 | 0.9573 | 0.079* | |
H21B | 0.8179 | 0.3091 | 1.0122 | 0.079* | |
C22 | 0.78256 (7) | 0.27180 (19) | 0.89508 (12) | 0.0541 (5) | |
C23 | 0.75253 (8) | 0.3758 (2) | 0.88893 (14) | 0.0665 (6) | |
H23 | 0.7593 | 0.4502 | 0.9219 | 0.080* | |
C24 | 0.71304 (8) | 0.3717 (2) | 0.83530 (17) | 0.0788 (7) | |
H24 | 0.6935 | 0.4431 | 0.8315 | 0.095* | |
C25 | 0.70248 (8) | 0.2622 (3) | 0.78734 (17) | 0.0793 (7) | |
H25 | 0.6757 | 0.2588 | 0.7510 | 0.095* | |
C26 | 0.73147 (9) | 0.1580 (2) | 0.79312 (17) | 0.0786 (7) | |
H26 | 0.7242 | 0.0835 | 0.7608 | 0.094* | |
C27 | 0.77146 (8) | 0.1622 (2) | 0.84644 (15) | 0.0666 (6) | |
H27 | 0.7910 | 0.0907 | 0.8496 | 0.080* | |
C41 | 0.92802 (5) | −0.07165 (15) | 0.65635 (10) | 0.0365 (4) | |
C42 | 0.95180 (6) | −0.18712 (15) | 0.66551 (11) | 0.0413 (4) | |
H42 | 0.9536 | −0.2276 | 0.7218 | 0.050* | |
C43 | 0.97284 (6) | −0.24233 (15) | 0.59168 (12) | 0.0418 (4) | |
C44 | 0.96955 (5) | −0.18406 (16) | 0.50760 (10) | 0.0397 (4) | |
C45 | 0.94445 (6) | −0.07142 (16) | 0.49729 (11) | 0.0457 (4) | |
H45 | 0.9413 | −0.0335 | 0.4403 | 0.055* | |
C46 | 0.92416 (6) | −0.01533 (16) | 0.57120 (10) | 0.0432 (4) | |
H46 | 0.9076 | 0.0613 | 0.5641 | 0.052* | |
Cl3 | 1.003610 (19) | −0.38412 (5) | 0.60745 (4) | 0.06910 (17) | |
Cl4 | 0.996849 (15) | −0.25042 (5) | 0.41501 (3) | 0.05514 (14) | |
N2 | 0.88577 (5) | 0.17874 (13) | 0.81121 (9) | 0.0429 (3) | |
N3 | 0.90549 (5) | 0.11577 (13) | 0.73954 (9) | 0.0420 (3) | |
H3 | 0.9165 | 0.1588 | 0.6947 | 0.050* | |
O5 | 0.89500 (5) | −0.07987 (13) | 0.80290 (9) | 0.0670 (4) | |
S1 | 0.928623 (15) | 0.39529 (4) | 0.74647 (3) | 0.05024 (14) | |
S2 | 0.868881 (19) | 0.38921 (5) | 0.90532 (4) | 0.06536 (17) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0380 (9) | 0.0442 (10) | 0.0473 (10) | 0.0024 (7) | −0.0007 (7) | −0.0127 (8) |
C4 | 0.0479 (9) | 0.0376 (9) | 0.0386 (9) | 0.0008 (7) | −0.0020 (7) | −0.0028 (7) |
C11 | 0.0582 (12) | 0.0384 (10) | 0.0873 (14) | 0.0044 (8) | −0.0031 (10) | 0.0042 (10) |
C12 | 0.0501 (11) | 0.0407 (9) | 0.0551 (11) | 0.0096 (8) | −0.0017 (8) | 0.0110 (8) |
C13 | 0.0547 (12) | 0.0626 (13) | 0.0586 (12) | −0.0006 (9) | −0.0006 (9) | 0.0055 (10) |
C14 | 0.0765 (15) | 0.0728 (16) | 0.0897 (17) | −0.0124 (12) | −0.0258 (14) | 0.0036 (14) |
C15 | 0.122 (2) | 0.0674 (16) | 0.0853 (19) | 0.0185 (16) | −0.0551 (18) | −0.0155 (14) |
C16 | 0.122 (2) | 0.093 (2) | 0.0470 (12) | 0.0580 (18) | −0.0124 (14) | 0.0022 (13) |
C17 | 0.0672 (13) | 0.0668 (13) | 0.0555 (12) | 0.0254 (10) | 0.0075 (10) | 0.0217 (11) |
C21 | 0.0715 (13) | 0.0794 (15) | 0.0463 (10) | 0.0154 (11) | 0.0151 (9) | −0.0054 (10) |
C22 | 0.0572 (11) | 0.0588 (12) | 0.0470 (10) | 0.0039 (9) | 0.0202 (8) | 0.0039 (9) |
C23 | 0.0691 (14) | 0.0589 (13) | 0.0718 (14) | 0.0053 (10) | 0.0133 (11) | −0.0012 (10) |
C24 | 0.0663 (15) | 0.0719 (16) | 0.0984 (18) | 0.0057 (11) | 0.0047 (13) | 0.0141 (13) |
C25 | 0.0638 (14) | 0.093 (2) | 0.0815 (16) | −0.0151 (13) | 0.0027 (12) | 0.0134 (14) |
C26 | 0.0741 (16) | 0.0746 (16) | 0.0876 (16) | −0.0222 (13) | 0.0202 (13) | −0.0112 (13) |
C27 | 0.0684 (14) | 0.0561 (13) | 0.0761 (14) | 0.0001 (10) | 0.0245 (11) | 0.0010 (11) |
C41 | 0.0394 (9) | 0.0308 (8) | 0.0391 (8) | 0.0002 (6) | −0.0021 (7) | −0.0031 (7) |
C42 | 0.0507 (10) | 0.0344 (8) | 0.0388 (9) | 0.0021 (7) | −0.0015 (7) | 0.0036 (7) |
C43 | 0.0414 (9) | 0.0312 (8) | 0.0527 (10) | 0.0047 (6) | 0.0003 (7) | −0.0004 (7) |
C44 | 0.0380 (9) | 0.0407 (9) | 0.0404 (9) | −0.0003 (7) | 0.0010 (7) | −0.0089 (7) |
C45 | 0.0574 (11) | 0.0451 (10) | 0.0344 (9) | 0.0045 (8) | −0.0044 (7) | 0.0022 (7) |
C46 | 0.0529 (10) | 0.0354 (9) | 0.0409 (9) | 0.0105 (7) | −0.0060 (7) | −0.0009 (7) |
Cl3 | 0.0829 (4) | 0.0453 (3) | 0.0796 (4) | 0.0294 (2) | 0.0159 (3) | 0.0084 (2) |
Cl4 | 0.0530 (3) | 0.0620 (3) | 0.0507 (3) | 0.0041 (2) | 0.0078 (2) | −0.0163 (2) |
N2 | 0.0453 (8) | 0.0432 (8) | 0.0403 (8) | 0.0035 (6) | 0.0040 (6) | −0.0102 (6) |
N3 | 0.0530 (9) | 0.0344 (7) | 0.0390 (7) | 0.0019 (6) | 0.0109 (6) | −0.0051 (6) |
O5 | 0.1092 (12) | 0.0441 (8) | 0.0484 (7) | −0.0026 (7) | 0.0231 (7) | 0.0029 (6) |
S1 | 0.0421 (3) | 0.0425 (2) | 0.0661 (3) | −0.00378 (18) | 0.0001 (2) | −0.0080 (2) |
S2 | 0.0633 (3) | 0.0652 (3) | 0.0678 (3) | 0.0036 (2) | 0.0078 (2) | −0.0361 (3) |
Geometric parameters (Å, º) top
C1—N2 | 1.270 (2) | C22—C27 | 1.378 (3) |
C1—S2 | 1.7421 (16) | C22—C23 | 1.383 (3) |
C1—S1 | 1.7815 (18) | C23—C24 | 1.371 (3) |
C4—O5 | 1.210 (2) | C23—H23 | 0.9300 |
C4—N3 | 1.353 (2) | C24—C25 | 1.369 (3) |
C4—C41 | 1.491 (2) | C24—H24 | 0.9300 |
C11—C12 | 1.488 (3) | C25—C26 | 1.365 (3) |
C11—S1 | 1.8363 (19) | C25—H25 | 0.9300 |
C11—H11A | 0.9700 | C26—C27 | 1.380 (3) |
C11—H11B | 0.9700 | C26—H26 | 0.9300 |
C12—C17 | 1.377 (3) | C27—H27 | 0.9300 |
C12—C13 | 1.387 (3) | C41—C42 | 1.384 (2) |
C13—C14 | 1.363 (3) | C41—C46 | 1.385 (2) |
C13—H13 | 0.9300 | C42—C43 | 1.376 (2) |
C14—C15 | 1.367 (4) | C42—H42 | 0.9300 |
C14—H14 | 0.9300 | C43—C44 | 1.379 (2) |
C15—C16 | 1.376 (4) | C43—Cl3 | 1.7287 (15) |
C15—H15 | 0.9300 | C44—C45 | 1.379 (2) |
C16—C17 | 1.372 (4) | C44—Cl4 | 1.7254 (16) |
C16—H16 | 0.9300 | C45—C46 | 1.371 (2) |
C17—H17 | 0.9300 | C45—H45 | 0.9300 |
C21—C22 | 1.489 (3) | C46—H46 | 0.9300 |
C21—S2 | 1.814 (2) | N2—N3 | 1.3703 (18) |
C21—H21A | 0.9700 | N3—H3 | 0.8600 |
C21—H21B | 0.9700 | | |
| | | |
N2—C1—S2 | 121.15 (13) | C24—C23—C22 | 121.4 (2) |
N2—C1—S1 | 126.79 (12) | C24—C23—H23 | 119.3 |
S2—C1—S1 | 111.96 (10) | C22—C23—H23 | 119.3 |
O5—C4—N3 | 123.16 (15) | C25—C24—C23 | 119.8 (2) |
O5—C4—C41 | 122.39 (15) | C25—C24—H24 | 120.1 |
N3—C4—C41 | 114.42 (14) | C23—C24—H24 | 120.1 |
C12—C11—S1 | 112.36 (13) | C26—C25—C24 | 119.7 (2) |
C12—C11—H11A | 109.1 | C26—C25—H25 | 120.2 |
S1—C11—H11A | 109.1 | C24—C25—H25 | 120.2 |
C12—C11—H11B | 109.1 | C25—C26—C27 | 120.7 (2) |
S1—C11—H11B | 109.1 | C25—C26—H26 | 119.6 |
H11A—C11—H11B | 107.9 | C27—C26—H26 | 119.6 |
C17—C12—C13 | 118.84 (19) | C22—C27—C26 | 120.3 (2) |
C17—C12—C11 | 120.49 (18) | C22—C27—H27 | 119.9 |
C13—C12—C11 | 120.65 (18) | C26—C27—H27 | 119.9 |
C14—C13—C12 | 120.9 (2) | C42—C41—C46 | 119.03 (15) |
C14—C13—H13 | 119.6 | C42—C41—C4 | 117.61 (14) |
C12—C13—H13 | 119.6 | C46—C41—C4 | 123.36 (14) |
C13—C14—C15 | 119.5 (2) | C43—C42—C41 | 120.32 (15) |
C13—C14—H14 | 120.3 | C43—C42—H42 | 119.8 |
C15—C14—H14 | 120.3 | C41—C42—H42 | 119.8 |
C14—C15—C16 | 120.8 (2) | C42—C43—C44 | 120.11 (14) |
C14—C15—H15 | 119.6 | C42—C43—Cl3 | 118.50 (13) |
C16—C15—H15 | 119.6 | C44—C43—Cl3 | 121.39 (13) |
C17—C16—C15 | 119.4 (2) | C43—C44—C45 | 119.88 (15) |
C17—C16—H16 | 120.3 | C43—C44—Cl4 | 120.56 (13) |
C15—C16—H16 | 120.3 | C45—C44—Cl4 | 119.56 (13) |
C16—C17—C12 | 120.5 (2) | C46—C45—C44 | 119.95 (15) |
C16—C17—H17 | 119.7 | C46—C45—H45 | 120.0 |
C12—C17—H17 | 119.7 | C44—C45—H45 | 120.0 |
C22—C21—S2 | 113.05 (14) | C45—C46—C41 | 120.66 (15) |
C22—C21—H21A | 109.0 | C45—C46—H46 | 119.7 |
S2—C21—H21A | 109.0 | C41—C46—H46 | 119.7 |
C22—C21—H21B | 109.0 | C1—N2—N3 | 117.31 (14) |
S2—C21—H21B | 109.0 | C4—N3—N2 | 119.57 (14) |
H21A—C21—H21B | 107.8 | C4—N3—H3 | 120.2 |
C27—C22—C23 | 118.1 (2) | N2—N3—H3 | 120.2 |
C27—C22—C21 | 121.56 (19) | C1—S1—C11 | 99.03 (9) |
C23—C22—C21 | 120.32 (19) | C1—S2—C21 | 102.90 (9) |
| | | |
S1—C11—C12—C17 | −81.40 (19) | C46—C41—C42—C43 | 2.6 (2) |
S1—C11—C12—C13 | 97.03 (18) | C4—C41—C42—C43 | −177.73 (14) |
C17—C12—C13—C14 | 0.4 (3) | C41—C42—C43—C44 | −1.3 (2) |
C11—C12—C13—C14 | −178.04 (18) | C41—C42—C43—Cl3 | 178.06 (12) |
C12—C13—C14—C15 | −0.6 (3) | C42—C43—C44—C45 | −1.1 (2) |
C13—C14—C15—C16 | 0.3 (4) | Cl3—C43—C44—C45 | 179.57 (13) |
C14—C15—C16—C17 | 0.0 (3) | C42—C43—C44—Cl4 | 178.56 (12) |
C15—C16—C17—C12 | −0.2 (3) | Cl3—C43—C44—Cl4 | −0.8 (2) |
C13—C12—C17—C16 | −0.1 (3) | C43—C44—C45—C46 | 2.2 (2) |
C11—C12—C17—C16 | 178.41 (17) | Cl4—C44—C45—C46 | −177.47 (13) |
S2—C21—C22—C27 | 109.86 (19) | C44—C45—C46—C41 | −0.9 (3) |
S2—C21—C22—C23 | −69.2 (2) | C42—C41—C46—C45 | −1.5 (2) |
C27—C22—C23—C24 | −0.8 (3) | C4—C41—C46—C45 | 178.85 (15) |
C21—C22—C23—C24 | 178.2 (2) | S2—C1—N2—N3 | 179.53 (11) |
C22—C23—C24—C25 | 0.8 (4) | S1—C1—N2—N3 | −4.4 (2) |
C23—C24—C25—C26 | −0.2 (4) | O5—C4—N3—N2 | −4.1 (2) |
C24—C25—C26—C27 | −0.4 (4) | C41—C4—N3—N2 | 177.63 (13) |
C23—C22—C27—C26 | 0.3 (3) | C1—N2—N3—C4 | 166.39 (15) |
C21—C22—C27—C26 | −178.79 (19) | N2—C1—S1—C11 | 102.89 (16) |
C25—C26—C27—C22 | 0.3 (3) | S2—C1—S1—C11 | −80.72 (10) |
O5—C4—C41—C42 | −28.8 (2) | C12—C11—S1—C1 | −69.67 (16) |
N3—C4—C41—C42 | 149.45 (15) | N2—C1—S2—C21 | −14.24 (16) |
O5—C4—C41—C46 | 150.88 (17) | S1—C1—S2—C21 | 169.14 (9) |
N3—C4—C41—C46 | −30.8 (2) | C22—C21—S2—C1 | −77.00 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···S1 | 0.86 | 2.59 | 2.9751 (14) | 108 |
C16—H16···O5i | 0.93 | 2.44 | 3.294 (3) | 153 |
Symmetry code: (i) x, −y, z−1/2. |
(D3) dimethyl (3,4-dichlorobenzoyl)-1-methylcarbonohydrazonodithioate
top
Crystal data top
C11H12Cl2N2OS2 | Z = 2 |
Mr = 323.25 | F(000) = 332 |
Triclinic, P1 | Dx = 1.516 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9307 (4) Å | Cell parameters from 7920 reflections |
b = 9.0858 (7) Å | θ = 2.2–36.1° |
c = 10.3873 (5) Å | µ = 0.74 mm−1 |
α = 65.039 (6)° | T = 291 K |
β = 69.172 (4)° | Prism, colourless |
γ = 74.892 (5)° | 0.5 × 0.35 × 0.2 mm |
V = 708.08 (7) Å3 | |
Data collection top
Kuma KM-4 CCD diffractometer | 2494 independent reflections |
Radiation source: fine-focus sealed tube | 2181 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scan | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | h = −10→9 |
Tmin = 0.447, Tmax = 1.000 | k = −10→10 |
10270 measured reflections | l = −12→12 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.067P)2] where P = (Fo2 + 2Fc2)/3 |
2494 reflections | (Δ/σ)max < 0.001 |
166 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
C11H12Cl2N2OS2 | γ = 74.892 (5)° |
Mr = 323.25 | V = 708.08 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9307 (4) Å | Mo Kα radiation |
b = 9.0858 (7) Å | µ = 0.74 mm−1 |
c = 10.3873 (5) Å | T = 291 K |
α = 65.039 (6)° | 0.5 × 0.35 × 0.2 mm |
β = 69.172 (4)° | |
Data collection top
Kuma KM-4 CCD diffractometer | 2494 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 2181 reflections with I > 2σ(I) |
Tmin = 0.447, Tmax = 1.000 | Rint = 0.034 |
10270 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.24 e Å−3 |
2494 reflections | Δρmin = −0.42 e Å−3 |
166 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.34457 (5) | 0.64354 (5) | 0.39398 (5) | 0.03415 (16) | |
S2 | 0.55683 (6) | 0.41504 (6) | 0.24205 (5) | 0.04409 (17) | |
Cl3 | 0.01705 (7) | −0.22745 (7) | 0.98208 (6) | 0.0633 (2) | |
Cl4 | 0.29864 (8) | −0.15136 (8) | 1.04992 (6) | 0.0642 (2) | |
N2 | 0.24742 (16) | 0.39595 (16) | 0.39517 (15) | 0.0317 (3) | |
N3 | 0.27827 (18) | 0.26883 (17) | 0.33799 (15) | 0.0341 (3) | |
O5 | 0.20495 (17) | 0.02531 (16) | 0.39643 (15) | 0.0452 (3) | |
C1 | 0.3683 (2) | 0.47383 (19) | 0.34812 (17) | 0.0288 (4) | |
C3 | 0.2550 (3) | 0.3256 (3) | 0.1920 (2) | 0.0510 (5) | |
H3A | 0.2957 | 0.2391 | 0.1536 | 0.076* | |
H3B | 0.3122 | 0.4180 | 0.1269 | 0.076* | |
H3C | 0.1419 | 0.3571 | 0.1991 | 0.076* | |
C4 | 0.2390 (2) | 0.1188 (2) | 0.43512 (19) | 0.0324 (4) | |
C11 | 0.1332 (2) | 0.6634 (3) | 0.4821 (3) | 0.0526 (5) | |
H11A | 0.0752 | 0.6813 | 0.4136 | 0.079* | |
H11B | 0.1035 | 0.7546 | 0.5140 | 0.079* | |
H11C | 0.1068 | 0.5650 | 0.5662 | 0.079* | |
C21 | 0.6750 (2) | 0.5691 (3) | 0.2005 (2) | 0.0523 (5) | |
H21A | 0.6319 | 0.6725 | 0.1386 | 0.078* | |
H21B | 0.7847 | 0.5404 | 0.1498 | 0.078* | |
H21C | 0.6717 | 0.5770 | 0.2907 | 0.078* | |
C41 | 0.24920 (19) | 0.06592 (19) | 0.58904 (18) | 0.0297 (4) | |
C42 | 0.1396 (2) | −0.0342 (2) | 0.70192 (19) | 0.0342 (4) | |
H42 | 0.0565 | −0.0572 | 0.6819 | 0.041* | |
C43 | 0.1531 (2) | −0.0998 (2) | 0.8434 (2) | 0.0379 (4) | |
C44 | 0.2777 (2) | −0.0674 (2) | 0.87326 (19) | 0.0384 (4) | |
C45 | 0.3871 (2) | 0.0300 (2) | 0.7616 (2) | 0.0386 (4) | |
H45 | 0.4715 | 0.0505 | 0.7817 | 0.046* | |
C46 | 0.3736 (2) | 0.0980 (2) | 0.6196 (2) | 0.0342 (4) | |
H46 | 0.4478 | 0.1655 | 0.5443 | 0.041* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0358 (3) | 0.0255 (2) | 0.0420 (3) | −0.01139 (19) | −0.00882 (19) | −0.01049 (19) |
S2 | 0.0378 (3) | 0.0416 (3) | 0.0486 (3) | −0.0114 (2) | 0.0010 (2) | −0.0197 (2) |
Cl3 | 0.0585 (4) | 0.0588 (4) | 0.0508 (3) | −0.0313 (3) | −0.0033 (2) | 0.0041 (3) |
Cl4 | 0.0743 (4) | 0.0669 (4) | 0.0420 (3) | −0.0148 (3) | −0.0256 (3) | −0.0002 (3) |
N2 | 0.0354 (8) | 0.0212 (7) | 0.0374 (8) | −0.0078 (6) | −0.0100 (6) | −0.0076 (6) |
N3 | 0.0445 (9) | 0.0264 (7) | 0.0339 (7) | −0.0124 (6) | −0.0123 (6) | −0.0078 (6) |
O5 | 0.0603 (9) | 0.0348 (7) | 0.0512 (8) | −0.0205 (6) | −0.0165 (6) | −0.0165 (6) |
C1 | 0.0327 (9) | 0.0214 (8) | 0.0287 (8) | −0.0066 (7) | −0.0098 (6) | −0.0029 (6) |
C3 | 0.0724 (15) | 0.0456 (12) | 0.0403 (10) | −0.0184 (11) | −0.0216 (10) | −0.0097 (9) |
C4 | 0.0318 (9) | 0.0270 (9) | 0.0396 (9) | −0.0074 (7) | −0.0093 (7) | −0.0117 (7) |
C11 | 0.0389 (11) | 0.0379 (11) | 0.0822 (15) | −0.0053 (9) | −0.0067 (10) | −0.0312 (11) |
C21 | 0.0406 (11) | 0.0613 (14) | 0.0505 (11) | −0.0256 (10) | 0.0006 (9) | −0.0163 (10) |
C41 | 0.0312 (9) | 0.0191 (8) | 0.0380 (9) | −0.0039 (7) | −0.0102 (7) | −0.0091 (7) |
C42 | 0.0316 (9) | 0.0253 (9) | 0.0446 (10) | −0.0070 (7) | −0.0100 (7) | −0.0106 (8) |
C43 | 0.0371 (10) | 0.0254 (9) | 0.0418 (10) | −0.0085 (7) | −0.0055 (8) | −0.0056 (7) |
C44 | 0.0434 (11) | 0.0295 (9) | 0.0372 (9) | −0.0020 (8) | −0.0146 (8) | −0.0064 (8) |
C45 | 0.0391 (10) | 0.0310 (9) | 0.0482 (10) | −0.0070 (8) | −0.0185 (8) | −0.0103 (8) |
C46 | 0.0331 (9) | 0.0245 (9) | 0.0422 (9) | −0.0093 (7) | −0.0093 (7) | −0.0075 (7) |
Geometric parameters (Å, º) top
S1—C1 | 1.7400 (17) | C11—H11A | 0.9600 |
S1—C11 | 1.7796 (19) | C11—H11B | 0.9600 |
S2—C1 | 1.7446 (17) | C11—H11C | 0.9600 |
S2—C21 | 1.787 (2) | C21—H21A | 0.9600 |
Cl3—C43 | 1.7254 (17) | C21—H21B | 0.9600 |
Cl4—C44 | 1.7241 (17) | C21—H21C | 0.9600 |
N2—C1 | 1.279 (2) | C41—C42 | 1.382 (2) |
N2—N3 | 1.435 (2) | C41—C46 | 1.385 (2) |
N3—C4 | 1.355 (2) | C42—C43 | 1.371 (2) |
N3—C3 | 1.455 (2) | C42—H42 | 0.9300 |
O5—C4 | 1.219 (2) | C43—C44 | 1.383 (3) |
C3—H3A | 0.9600 | C44—C45 | 1.365 (3) |
C3—H3B | 0.9600 | C45—C46 | 1.375 (2) |
C3—H3C | 0.9600 | C45—H45 | 0.9300 |
C4—C41 | 1.493 (2) | C46—H46 | 0.9300 |
| | | |
C1—S1—C11 | 100.95 (9) | S2—C21—H21A | 109.5 |
C1—S2—C21 | 103.86 (9) | S2—C21—H21B | 109.5 |
C1—N2—N3 | 113.06 (13) | H21A—C21—H21B | 109.5 |
C4—N3—N2 | 117.87 (14) | S2—C21—H21C | 109.5 |
C4—N3—C3 | 118.05 (15) | H21A—C21—H21C | 109.5 |
N2—N3—C3 | 114.10 (14) | H21B—C21—H21C | 109.5 |
N2—C1—S1 | 118.69 (13) | C42—C41—C46 | 119.55 (16) |
N2—C1—S2 | 122.66 (13) | C42—C41—C4 | 117.54 (15) |
S1—C1—S2 | 118.64 (9) | C46—C41—C4 | 122.50 (15) |
N3—C3—H3A | 109.5 | C43—C42—C41 | 120.11 (16) |
N3—C3—H3B | 109.5 | C43—C42—H42 | 119.9 |
H3A—C3—H3B | 109.5 | C41—C42—H42 | 119.9 |
N3—C3—H3C | 109.5 | C42—C43—C44 | 120.10 (16) |
H3A—C3—H3C | 109.5 | C42—C43—Cl3 | 119.35 (14) |
H3B—C3—H3C | 109.5 | C44—C43—Cl3 | 120.52 (14) |
O5—C4—N3 | 121.20 (16) | C45—C44—C43 | 119.84 (16) |
O5—C4—C41 | 120.43 (16) | C45—C44—Cl4 | 119.35 (15) |
N3—C4—C41 | 118.24 (15) | C43—C44—Cl4 | 120.80 (14) |
S1—C11—H11A | 109.5 | C44—C45—C46 | 120.58 (17) |
S1—C11—H11B | 109.5 | C44—C45—H45 | 119.7 |
H11A—C11—H11B | 109.5 | C46—C45—H45 | 119.7 |
S1—C11—H11C | 109.5 | C45—C46—C41 | 119.81 (16) |
H11A—C11—H11C | 109.5 | C45—C46—H46 | 120.1 |
H11B—C11—H11C | 109.5 | C41—C46—H46 | 120.1 |
| | | |
C1—N2—N3—C4 | 131.65 (16) | N3—C4—C41—C46 | −40.2 (2) |
C1—N2—N3—C3 | −83.33 (18) | C46—C41—C42—C43 | 0.7 (3) |
N3—N2—C1—S1 | 174.34 (10) | C4—C41—C42—C43 | 173.53 (16) |
N3—N2—C1—S2 | −6.62 (19) | C41—C42—C43—C44 | −0.7 (3) |
C11—S1—C1—N2 | −6.69 (16) | C41—C42—C43—Cl3 | −178.87 (14) |
C11—S1—C1—S2 | 174.23 (11) | C42—C43—C44—C45 | 0.0 (3) |
C21—S2—C1—N2 | 177.38 (14) | Cl3—C43—C44—C45 | 178.12 (15) |
C21—S2—C1—S1 | −3.59 (13) | C42—C43—C44—Cl4 | −178.98 (14) |
N2—N3—C4—O5 | 152.86 (16) | Cl3—C43—C44—Cl4 | −0.9 (2) |
C3—N3—C4—O5 | 9.2 (3) | C43—C44—C45—C46 | 0.8 (3) |
N2—N3—C4—C41 | −31.2 (2) | Cl4—C44—C45—C46 | 179.77 (14) |
C3—N3—C4—C41 | −174.87 (16) | C44—C45—C46—C41 | −0.8 (3) |
O5—C4—C41—C42 | −36.9 (2) | C42—C41—C46—C45 | 0.1 (2) |
N3—C4—C41—C42 | 147.19 (16) | C4—C41—C46—C45 | −172.39 (17) |
O5—C4—C41—C46 | 135.75 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11B···O5i | 0.96 | 2.49 | 3.200 (2) | 131 |
Symmetry code: (i) x, y+1, z. |
(D4) 3,4-dichloro-
N'-(1,3-dithiolan-2-ylidene)-
N-methylbenzohydrazide
top
Crystal data top
C11H10Cl2N2OS2 | F(000) = 656 |
Mr = 321.23 | Dx = 1.497 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 9990 reflections |
a = 13.3680 (2) Å | θ = 3.4–69.4° |
b = 8.1817 (1) Å | µ = 6.76 mm−1 |
c = 13.5158 (2) Å | T = 296 K |
β = 105.415 (1)° | Plate, colourless |
V = 1425.08 (3) Å3 | 0.3 × 0.2 × 0.05 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD diffractometer | 2643 independent reflections |
Radiation source: fine-focus sealed tube | 2589 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scan | θmax = 69.8°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −16→15 |
Tmin = 0.423, Tmax = 0.753 | k = −9→9 |
15835 measured reflections | l = −16→16 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0549P)2 + 0.5411P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
2643 reflections | Δρmax = 0.48 e Å−3 |
165 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0058 (6) |
Crystal data top
C11H10Cl2N2OS2 | V = 1425.08 (3) Å3 |
Mr = 321.23 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 13.3680 (2) Å | µ = 6.76 mm−1 |
b = 8.1817 (1) Å | T = 296 K |
c = 13.5158 (2) Å | 0.3 × 0.2 × 0.05 mm |
β = 105.415 (1)° | |
Data collection top
Bruker SMART APEX CCD diffractometer | 2643 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2589 reflections with I > 2σ(I) |
Tmin = 0.423, Tmax = 0.753 | Rint = 0.034 |
15835 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.48 e Å−3 |
2643 reflections | Δρmin = −0.36 e Å−3 |
165 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.83398 (12) | −0.10963 (19) | 0.62822 (12) | 0.0388 (4) | |
C3 | 1.02049 (16) | −0.0263 (3) | 0.80548 (17) | 0.0591 (5) | |
H3A | 1.0585 | 0.0739 | 0.8081 | 0.089* | |
H3B | 1.0348 | −0.0966 | 0.7540 | 0.089* | |
H3C | 1.0412 | −0.0795 | 0.8711 | 0.089* | |
C4 | 0.87322 (16) | 0.1061 (2) | 0.84450 (14) | 0.0493 (4) | |
C11 | 0.8095 (2) | −0.2119 (3) | 0.44131 (16) | 0.0639 (6) | |
H11A | 0.8756 | −0.2665 | 0.4492 | 0.077* | |
H11B | 0.7618 | −0.2500 | 0.3783 | 0.077* | |
C21 | 0.8232 (2) | −0.0316 (3) | 0.43692 (16) | 0.0679 (6) | |
H21A | 0.7562 | 0.0207 | 0.4110 | 0.081* | |
H21B | 0.8658 | −0.0058 | 0.3910 | 0.081* | |
C41 | 0.75852 (16) | 0.1172 (2) | 0.83001 (14) | 0.0485 (4) | |
C42 | 0.72354 (18) | 0.1218 (3) | 0.91825 (16) | 0.0584 (5) | |
H42 | 0.7712 | 0.1182 | 0.9824 | 0.070* | |
C43 | 0.6195 (2) | 0.1316 (3) | 0.91151 (19) | 0.0732 (7) | |
H43 | 0.5970 | 0.1319 | 0.9709 | 0.088* | |
C44 | 0.54807 (19) | 0.1410 (3) | 0.8166 (2) | 0.0736 (7) | |
C45 | 0.58224 (18) | 0.1418 (3) | 0.72798 (17) | 0.0657 (6) | |
C46 | 0.68686 (16) | 0.1289 (3) | 0.73480 (15) | 0.0561 (5) | |
H46 | 0.7094 | 0.1280 | 0.6754 | 0.067* | |
Cl4 | 0.41784 (6) | 0.15325 (17) | 0.80980 (7) | 0.1283 (4) | |
Cl5 | 0.49472 (5) | 0.15578 (13) | 0.60858 (5) | 0.1029 (3) | |
N2 | 0.84424 (11) | −0.11848 (17) | 0.72499 (11) | 0.0432 (3) | |
N3 | 0.90917 (11) | 0.00931 (19) | 0.77988 (11) | 0.0453 (3) | |
O5 | 0.93346 (13) | 0.1847 (2) | 0.91231 (12) | 0.0700 (4) | |
S1 | 0.75887 (4) | −0.25764 (6) | 0.54888 (3) | 0.04834 (17) | |
S2 | 0.88505 (4) | 0.04250 (6) | 0.56470 (3) | 0.05213 (18) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0401 (8) | 0.0359 (8) | 0.0427 (9) | 0.0021 (6) | 0.0149 (7) | −0.0013 (6) |
C3 | 0.0490 (10) | 0.0629 (12) | 0.0616 (12) | 0.0018 (9) | 0.0077 (9) | −0.0093 (10) |
C4 | 0.0621 (11) | 0.0403 (9) | 0.0437 (9) | 0.0033 (8) | 0.0109 (8) | −0.0023 (7) |
C11 | 0.0866 (15) | 0.0639 (13) | 0.0463 (11) | −0.0067 (11) | 0.0266 (10) | −0.0087 (9) |
C21 | 0.0981 (17) | 0.0641 (13) | 0.0442 (10) | −0.0131 (12) | 0.0237 (11) | 0.0016 (9) |
C41 | 0.0633 (11) | 0.0384 (9) | 0.0452 (9) | 0.0059 (8) | 0.0166 (8) | −0.0024 (7) |
C42 | 0.0764 (13) | 0.0541 (11) | 0.0463 (10) | 0.0046 (9) | 0.0191 (9) | −0.0048 (8) |
C43 | 0.0893 (17) | 0.0839 (17) | 0.0576 (12) | 0.0076 (13) | 0.0393 (12) | −0.0056 (11) |
C44 | 0.0665 (14) | 0.0930 (18) | 0.0698 (14) | 0.0143 (12) | 0.0330 (11) | −0.0036 (13) |
C45 | 0.0616 (12) | 0.0822 (16) | 0.0546 (12) | 0.0188 (11) | 0.0179 (10) | 0.0024 (10) |
C46 | 0.0616 (12) | 0.0640 (12) | 0.0462 (10) | 0.0137 (9) | 0.0202 (9) | 0.0014 (9) |
Cl4 | 0.0730 (5) | 0.2172 (12) | 0.1092 (6) | 0.0254 (6) | 0.0495 (4) | −0.0057 (7) |
Cl5 | 0.0651 (4) | 0.1753 (9) | 0.0641 (4) | 0.0303 (4) | 0.0098 (3) | 0.0085 (4) |
N2 | 0.0502 (8) | 0.0405 (8) | 0.0403 (7) | −0.0036 (6) | 0.0145 (6) | −0.0032 (6) |
N3 | 0.0492 (8) | 0.0432 (8) | 0.0421 (7) | −0.0018 (6) | 0.0101 (6) | −0.0055 (6) |
O5 | 0.0707 (9) | 0.0658 (9) | 0.0661 (9) | −0.0011 (8) | 0.0050 (7) | −0.0276 (8) |
S1 | 0.0532 (3) | 0.0483 (3) | 0.0446 (3) | −0.01043 (18) | 0.0151 (2) | −0.00656 (17) |
S2 | 0.0676 (3) | 0.0443 (3) | 0.0466 (3) | −0.01131 (19) | 0.0189 (2) | 0.00167 (17) |
Geometric parameters (Å, º) top
C1—N2 | 1.280 (2) | C21—H21A | 0.9700 |
C1—S1 | 1.7470 (17) | C21—H21B | 0.9700 |
C1—S2 | 1.7504 (16) | C41—C46 | 1.388 (3) |
C3—N3 | 1.465 (2) | C41—C42 | 1.392 (3) |
C3—H3A | 0.9600 | C42—C43 | 1.371 (3) |
C3—H3B | 0.9600 | C42—H42 | 0.9300 |
C3—H3C | 0.9600 | C43—C44 | 1.383 (4) |
C4—O5 | 1.229 (2) | C43—H43 | 0.9300 |
C4—N3 | 1.358 (2) | C44—C45 | 1.391 (3) |
C4—C41 | 1.496 (3) | C44—Cl4 | 1.722 (2) |
C11—C21 | 1.489 (3) | C45—C46 | 1.381 (3) |
C11—S1 | 1.799 (2) | C45—Cl5 | 1.727 (2) |
C11—H11A | 0.9700 | C46—H46 | 0.9300 |
C11—H11B | 0.9700 | N2—N3 | 1.433 (2) |
C21—S2 | 1.810 (2) | | |
| | | |
N2—C1—S1 | 118.42 (13) | C46—C41—C42 | 119.08 (19) |
N2—C1—S2 | 126.25 (13) | C46—C41—C4 | 123.79 (17) |
S1—C1—S2 | 115.30 (9) | C42—C41—C4 | 117.09 (18) |
N3—C3—H3A | 109.5 | C43—C42—C41 | 120.7 (2) |
N3—C3—H3B | 109.5 | C43—C42—H42 | 119.7 |
H3A—C3—H3B | 109.5 | C41—C42—H42 | 119.7 |
N3—C3—H3C | 109.5 | C42—C43—C44 | 120.2 (2) |
H3A—C3—H3C | 109.5 | C42—C43—H43 | 119.9 |
H3B—C3—H3C | 109.5 | C44—C43—H43 | 119.9 |
O5—C4—N3 | 120.73 (18) | C43—C44—C45 | 119.7 (2) |
O5—C4—C41 | 120.79 (17) | C43—C44—Cl4 | 119.49 (18) |
N3—C4—C41 | 118.47 (16) | C45—C44—Cl4 | 120.8 (2) |
C21—C11—S1 | 108.36 (15) | C46—C45—C44 | 120.0 (2) |
C21—C11—H11A | 110.0 | C46—C45—Cl5 | 119.34 (16) |
S1—C11—H11A | 110.0 | C44—C45—Cl5 | 120.61 (19) |
C21—C11—H11B | 110.0 | C45—C46—C41 | 120.28 (18) |
S1—C11—H11B | 110.0 | C45—C46—H46 | 119.9 |
H11A—C11—H11B | 108.4 | C41—C46—H46 | 119.9 |
C11—C21—S2 | 108.89 (15) | C1—N2—N3 | 111.92 (14) |
C11—C21—H21A | 109.9 | C4—N3—N2 | 119.29 (15) |
S2—C21—H21A | 109.9 | C4—N3—C3 | 118.37 (15) |
C11—C21—H21B | 109.9 | N2—N3—C3 | 114.50 (14) |
S2—C21—H21B | 109.9 | C1—S1—C11 | 94.22 (9) |
H21A—C21—H21B | 108.3 | C1—S2—C21 | 95.22 (9) |
| | | |
S1—C11—C21—S2 | 45.5 (2) | C42—C41—C46—C45 | −1.2 (3) |
O5—C4—C41—C46 | 137.3 (2) | C4—C41—C46—C45 | −178.8 (2) |
N3—C4—C41—C46 | −41.6 (3) | S1—C1—N2—N3 | 179.03 (11) |
O5—C4—C41—C42 | −40.3 (3) | S2—C1—N2—N3 | −3.2 (2) |
N3—C4—C41—C42 | 140.79 (18) | O5—C4—N3—N2 | 159.99 (18) |
C46—C41—C42—C43 | 2.4 (3) | C41—C4—N3—N2 | −21.1 (2) |
C4—C41—C42—C43 | −179.9 (2) | O5—C4—N3—C3 | 12.5 (3) |
C41—C42—C43—C44 | −1.6 (4) | C41—C4—N3—C3 | −168.55 (17) |
C42—C43—C44—C45 | −0.5 (4) | C1—N2—N3—C4 | 126.49 (17) |
C42—C43—C44—Cl4 | −180.0 (2) | C1—N2—N3—C3 | −84.84 (19) |
C43—C44—C45—C46 | 1.7 (4) | N2—C1—S1—C11 | −163.57 (15) |
Cl4—C44—C45—C46 | −178.8 (2) | S2—C1—S1—C11 | 18.41 (12) |
C43—C44—C45—Cl5 | −179.3 (2) | C21—C11—S1—C1 | −38.39 (19) |
Cl4—C44—C45—Cl5 | 0.2 (4) | N2—C1—S2—C21 | −174.89 (17) |
C44—C45—C46—C41 | −0.8 (4) | S1—C1—S2—C21 | 2.95 (13) |
Cl5—C45—C46—C41 | −179.89 (17) | C11—C21—S2—C1 | −29.4 (2) |
Experimental details
| (D1) | (D2) | (D3) | (D4) |
Crystal data |
Chemical formula | C10H10Cl2N2OS2 | C22H18Cl2N2OS2 | C11H12Cl2N2OS2 | C11H10Cl2N2OS2 |
Mr | 309.22 | 461.40 | 323.25 | 321.23 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, C2/c | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 296 | 292 | 291 | 296 |
a, b, c (Å) | 9.2225 (4), 11.2741 (5), 13.0892 (5) | 28.6760 (11), 10.3705 (3), 14.7176 (6) | 8.9307 (4), 9.0858 (7), 10.3873 (5) | 13.3680 (2), 8.1817 (1), 13.5158 (2) |
α, β, γ (°) | 90, 95.367 (1), 90 | 90, 90.900 (4), 90 | 65.039 (6), 69.172 (4), 74.892 (5) | 90, 105.415 (1), 90 |
V (Å3) | 1354.99 (10) | 4376.2 (3) | 708.08 (7) | 1425.08 (3) |
Z | 4 | 8 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Cu Kα |
µ (mm−1) | 0.77 | 0.50 | 0.74 | 6.76 |
Crystal size (mm) | 0.3 × 0.3 × 0.1 | 0.55 × 0.4 × 0.3 | 0.5 × 0.35 × 0.2 | 0.3 × 0.2 × 0.05 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD diffractometer | Kuma KM-4 CCD diffractometer | Kuma KM-4 CCD diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.914, 1.000 | 0.942, 1.000 | 0.447, 1.000 | 0.423, 0.753 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33334, 7766, 7138 | 17461, 3868, 3021 | 10270, 2494, 2181 | 15835, 2643, 2589 |
Rint | 0.021 | 0.022 | 0.034 | 0.034 |
(sin θ/λ)max (Å−1) | 0.700 | 0.595 | 0.595 | 0.609 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.092, 1.08 | 0.030, 0.084, 0.94 | 0.033, 0.097, 1.15 | 0.034, 0.100, 1.06 |
No. of reflections | 7766 | 3868 | 2494 | 2643 |
No. of parameters | 312 | 262 | 166 | 165 |
No. of restraints | 3 | 0 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.79, −0.31 | 0.22, −0.29 | 0.24, −0.42 | 0.48, −0.36 |
Absolute structure | Flack (1983), ???? Friedel pairs | ? | ? | ? |
Absolute structure parameter | −0.02 (4) | ? | ? | ? |
Hydrogen-bond geometry (Å, º) for (D1) top
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21E···Cl4Ai | 0.96 | 2.75 | 3.565 (3) | 143.5 |
N3A—H3A···O5ii | 0.86 | 2.10 | 2.8434 (18) | 143.9 |
N3—H3···O5A | 0.86 | 2.06 | 2.834 (2) | 148.9 |
N3—H3···S1 | 0.86 | 2.52 | 2.7810 (17) | 99 |
N3A—H3A···S1A | 0.86 | 2.49 | 2.8216 (16) | 104 |
Symmetry codes: (i) x+1, y, z+1; (ii) x−1, y, z. |
Hydrogen-bond geometry (Å, º) for (D2) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···S1 | 0.86 | 2.59 | 2.9751 (14) | 108.3 |
C16—H16···O5i | 0.93 | 2.44 | 3.294 (3) | 153.1 |
Symmetry code: (i) x, −y, z−1/2. |
Hydrogen-bond geometry (Å, º) for (D3) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11B···O5i | 0.96 | 2.49 | 3.200 (2) | 130.7 |
Symmetry code: (i) x, y+1, z. |
Selected bond lengths (Å) and torsion angles (°) for the title compounds topStructure | C1—N2—-N3–C4 | N2—N3—C4—C41 | N2—N3—C4—O5 | N2—N3 |
(D1) | -139.31 (18) | -177.95 (16) | 4.0 (3) | 1.416 (2) |
| -150.87 (17) | -178.19 (15) | 3.1 (3) | 1.402 (2) |
(D2) | 166.39 (15) | 177.63 (13) | -4.1 (2) | 1.3703 (18) |
(D3) | 131.65 (16) | -31.2 (2) | 152.86 (16) | 1.435 (2) |
(D4) | 126.49 (17) | -21.1 (2) | 159.99 (18) | 1.433 (2) |
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Because of the emergence of multi-drug-resistant strains of Mycobacterium tuberculosis in developed countries, significant efforts have been put into a search for new lead tuberculostatics. Among others, Foks and coworkers have synthesized hundreds of compounds, many of which showed reasonable activity against tuberculosis (Pancechowska-Ksepko et al., 1993; Milczarska et al., 1998, 1999; Foks et al., 2002; Gobis et al., 2011). Several crystal structures of selected representatives of these compounds were determined by our group in a search for relationships between activity and molecular structure (Główka et al., 2005; Olczak et al., 2007, 2011; Szczesio et al., 2011). The main working hypothesis tested in these studies was that planarity of a molecule is a prerequisite for tuberculostatic activity (Olczak et al., 2007). The hypothesis was based on an observation from our very first study on the molecular structure of 2-[amino(pyridine-2-yl)methylene]hydrazinecarbodithioic acid methyl ester in the crystalline state (Główka et al., 2005). This active compound in the crystal state exists in the zwitterionic form (formula A in Scheme 1) and it is planar (except for the terminal ester group) due to conjugations and intramolecular hydrogen bonds (Główka et al., 2005; Olczak et al., 2007; Orlewska et al., 2001). Surprisingly, overall planarity was also observed in the crystals of [amino(pyrazin-2-yl)methylene]carbonohydrazonodithioic acid diesters showing tuberculostatic activity (formula B in Scheme 1) (Olczak et al., 2011). Owing to the lack of an H atom at N3, the same intramolecular hydrogen-bond contacts as those observed in all type A (Scheme 1) structures could not be formed. Instead, another intramolecular hydrogen contact was observed, i.e. that between an amine group as a donor and an N atom at the ortho position of the pyrazine ring as an acceptor, similar to that observed in all pyrazinamide structures [Cambridge Structural Database (CSD), Version 5.32; Allen, 2002]. In the case of type B compounds (Scheme 1), planarity of the central structure frame (as evidenced by the torsion angle at the N—N bond) was secured by the conjugation alone (Olczak et al., 2011).
Next, the amine function in compounds of the types A and B has been replaced by a carbonyl group (compounds type C in Scheme 1), some of which also show promising activity (Foks et al., 2004; Sitarz et al., 2005). It was in accord with our hypothesis as the compounds could form similar intramolecular hydrogen bonds as in compounds of type A. The overall planarity of their molecules was confirmed in our studies on their crystal structures (Szczesio et al., 2011).
Our earlier observation that the conjugation in type B compounds was sufficient to secure planarity of the central molecular chain prompted us to synthesize the respective analogues D (Scheme 1), in which we have removed the last possibility of keeping the aromatic ring coplanar with the hydrazide fragment due to the intramolecular hydrogen bond N5—H···N(ring) (formula D in Scheme 1). We were encouraged by the structural characteristics of the well known agent isoniazid, in which also this intramolecular hydrogen bond could not be formed (Scheme 1). Most of the type B compounds show weak tuberculostatic activity (MIC about 50 mg ml-1) but for some the values are 20 times lower (Foks et al., 1992; Orlewska et al., 1995).
Here we report a study on the crystal structures of several type D compounds (Fig. 1–4), which differ in ester groups (Me, Bz or cyclic) or substitution by the methyl at the N3 atom (Scheme 2). There are seven diesters of benzoylcarbonohydrazonodithioic acid (CSD, Version 5.32; Allen, 2002). All are unsubstituted at the N3 atom. However, no mention has been made of their tuberculostatic activity in the papers.
In accord with our expectation, replacement of the aromatic ring containing an N atom in the ortho position by a phenyl resulted in its significant twist of 30–40° in comparison with planar 2-pyrazine or 2-pyrazine derivatives studied earlier. Similar values are observed in 19 benzamide structures found in the CSD, with an average of 22° (CSD, Version 5.32; Allen, 2002).
The other significant difference in the molecular structures of the D type and the formerly studied type C (Szczesio et al., 2011) compounds is the conformation around the N2—N3 bond. The absolute values of the respective torsion angle C1═N2—N3—C4 are close to 177° in two planar diesters of (pyrazine-2-carbonyl)carbonohydrazonodithioic acid (type C) (Szczesio et al., 2011) as compared with 166.39 (15)° in (D2), -139.31 (18) and -150.87 (17)° in (D1), 131.65 (16)° in (D3) and 126.49 (17)° in (D4) (Table 4). This means that structures (D1) and (D2) maintain approximate planarity with the aid of the N3—H···S intramolecular hydrogen-bond contact (Table 2). The lack of the hydrogen at the N3 atom in (D3) and (D4) results also in their very different conformation around their N3—C4 bonds in comparison with N3-unsubstituted aroylcarbonohydrazonodithioic acids esters (Table 4). The crucial torsion angle N2—N3—C4—C41 is about 180° in (D1) and (D2) and only 21–31° in (D3) and (D4), due to spatial repulsion introduced by the methyl in the latter structures. A similar difference is seen in the related torsion angle N2—N3—C4═O5, being about 4° in (D1) and (D2), and about 155° in (D3) and (D4), respectively (Table 4).
The question arises whether the observed differences in the molecular structures may be related to low tuberculostatic activity of the N3-substituted compounds. The fact is that only N3-unsubstituted derivatives show higher activity, especially (D1) (Gobis et al., 2011).
The differences in conformations along the main chain correlate with differences in the respective bond lengths (Table 4) indicating the change in conjugations. The largest difference is found for the N2—N3 bond length, which is 1.435 (2) Å (torsion about 130°) in (D3), 1.433 (2) Å (torsion about 125°) in (D4), 1.4143 (18) Å and 1.4017 (18) Å (torsion about -140° and -150°) in (D1) and 1.3703 (18) Å (torsion about 166°) in (D2) due to increasing (in the listed order) p(N3)—p(N2═C1) conjugation for the antiperiplanar (torsion about 180°) conformation.
Another interesting issue concerns the intramolecular N3—H···S hydrogen-bond contact possible in (D1) and (D2). Although the H···S distances of 2.49 and 2.52 Å in (D1) and 2.59 Å in (D2) are significantly shorter than the sum of their van der Waals radii (2.89 Å), the angles at the H atom are only 104, 99 and 108°, respectively. So, despite the H···S distances indicating hydrogen bonds, there is some doubt in the literature concerning contribution of the contacts to the stabilization energy of the crystals, especially because of the low values of the N3—H···S angles (Wood et al., 2009; Galek et al., 2010; Bilton et al., 2000). Our view on the subject has been presented in Szczesio et al. (2011).
In the studied crystals there are several intermolecular hydrogen bonds, some of which are quite strong and important for crystal packing (Figs. 5–7). In (D1), the two independent molecules form an infinite C22(8) chain [according to the graph-set definition of Bernstein et al. (1995)] parallel to the [100] direction through two intermolecular hydrogen bonds, viz. N3—H···O5A and N3A—H···O5(x-1, y, z). In addition, in (D1), there exists a C21—H···Cl4A(x+1, y, z) contact taking part in the formation of two additional chains, viz. C22(14) parallel to the [101] direction with an N3—H···O5A hydrogen bond and C22(16) parallel to the [001] direction with an N3A—H···O5(x-1, y, z) hydrogen bond. At the third level of the graph-set theory, the R66(38) ring formed by N3—H···O5A, N3A—H···O5(x-1, y, z) and C21—H···Cl4A(x+1, y, z) can be identified (Fig. 5). In (D2), there is only one weak hydrogen bond, C16—H···O5(x, -y, z-1/2), forming a C11(11) chain parallel to the [001] direction (Fig. 6). In (D3), there is also one weak hydrogen bond, C11—H..O5(x, y+1, z), forming a C11(8) chain parallel to the [010] direction (Fig. 7). No significant intermolecular contacts were observed in (D4).